Manufacture of gasolinelike hydrocarbons



Feb. 6, 1940. P. c. KEITH, JR

MANUFACTURE OF GASOLINELIKE HYDROCARBONS lOriginal Filed OGL 30, 1935 INVENTOR PERCIVAL C. KEITH JR.

M 3v. ,Swear-M.. v' ATTORNEY Patented Feb 6, 1940 UNITED sg'lATrasv MANUFACTUBE `F GASDLINELIKE HYDROCARBONS Percival C. Keith, Jr., Peapack, N. J., Miglior to Process Management Company, Inc., New yYork-N. Y., a corporation of Delaware.

Application October 30, 1935, Serial No. 47,1414

Renewed July 15, 1939 My invention relates to the vmanufacture of normally liquid gasolinelike hydrocarbons, that is to say, hydrocarbons having boiling points lying within a gasoline or motor-fuel boiling point range, from normally gaseous hydrocarbons of lower molecular weight, and more particularly to a process-for effecting the conversion or polymerization of hydrocarbon gases produced in the pyrolysis of hydrocarbon oils, and containing both saturated and unsaturated hydrocarbon constituents, to low-boiling, normally liquid gasolinelike products suitable for use as a motor fuel. s

The products of the pyrolysis of hydrocarbon oils include below the gasoline boiling-point range varying quantities of hydrogen, methane, ethane,

ethylene, propane, propylene, butane and butylenes, and as separated in oil-cracking operations the uncondensable gases may also contain limited quantities of heavier hydrocarbons such as pentane, hexane and other hydrocarbons having ve and six carbon atoms per molecule. It has been known in the art for some time that such gases can be polymerized to 'higher-boiling normally liquid non-aromatic products under high pressure and at temperatures ranging from about '750 to 1250 F.

My invention has for an object the provision of a'process of the character and for the purpose indicated, wherein' hydrocarbon gases such as 30 those produced in the-pyrolytic decomposition of hydrocarbon oils, after vseparationof .hydrogen and methane are converted to' normally liquid gasolinelike hydrocarbons of high" anti-knock value -when used as motor fuel, together ywith such additional operative improvements and advantages as may hereinafter be found to obtain. My invention contemplates a continuous and cyclic process forobtaining low-boiling hydrocarbon liquids of a gasolneli'ke nature from nor-V 40 mally gaseous hydrocarbons such as thoseproduced in the lpyrolysis or cracking of hydrocarbon oils, in which gases substantially free from hydrogen and methane are subjected to high pressures of from 500 to 3000 pounds per square inch or higher and temperatures ranging from about 750 to 1250* F. but preferably from about 1000 F. to about 1100 F. for a period of time suiiicient to eiect the desired polymerization reactions. The products of Vpolymerization are so cooled to effect the separation of normally liquid products of gasolinelike nature as well as any I have found that it is of great importance to fractionate the gases prior to such conversion to separate hydrogen and methane as .completely `as possible, and also where necessary to separate l with an oil-cracking unit, as will be made more -clear hereinbelow, the fractionation of the gaseous products of oil cracking may obviously be conducted in different manners4 prior to their use 15 for polymerization in .accordance with our process. Thus, in oil-cracking plants operated atlow pressures and producing relatively wet" gases, such gases may be fractionated after removal of the cracked gasoline in the manner indicated hereinabove, whereas in oil-cracking plants operating under high pressure, most or all of the constituents desired for polymerization.I may be actually removed from the condenser in liquid form with the gasoline, to be recovered in 25 the course of stabilization. In some instances, the overhead products from the cracked-gasoline stabilizer may even be suiiiciently free from hydrogen and methane' to require no further fractionation prior to conversion. In other-instances. 30 however, gases from the gas separator oi' .an oil-cracking unit may be combined with overhead or reflux from the gasoline stabilizer, thecombined products then being fractionated for the removal oi' hydrogen and methane (as well as 35 all or a portion of the ethane where desired) prior. to conversion. The particular fractionating methodemployed -will depend upon the composition of the normally gaseous products o1' cracking as well as the pressures and tempera- 40 tures underrwhich the condensation and separation of the cracked gasoline is en'ected. It will also depend tol some extent-on whether or not the recycled stock from the gas-conversion unit is separately fractionated or is recycled to the 45 oil-cracking operation for fractionation along with the products of cracking.

In order that'v my invention' may be fully set forth and understood, I now describe, with reference to the drawing accompanying and forming a part of this specification, a preferred form and manner in winch my invention may be practiced and embodied. In the drawing, The. single gure is a-inore or less diagrammatic elevational view of apparatus for effecting the polymerization oi hydrocarbon gases in accordance with my invention, including also apparatus for cracking hydrocarbon oils to produce motor fuel and gases for polymerization,` and illustrating an advantageous manner in which an oil-cracking unit may be combined with a gas-polymerizing unit operated in accordance with my invention.

In the instance illustrated in the drawing, I haveA shown an oil-cracking unit which is operated for the purpose of reforming naphtha, i. e., of converting naphtha of relatively low anti-knock value into motor fuel of higher anti-knock value.

As is well known, such a reforming operation' ordinarily results in the formation of considerable quantities of fixed gases and constituents lower boiling than are desired to be included in the final motor-fuel product. My process makes it possible to effect the conversion of such gaseous constituents exclusive ofv hydrogen and methane to hydrocarbon liquids useful as motor fuel and possessing extremely high anti-knock value, which may be blended, if desired, with the reformed gasoline produced in the cracking operation. While the gas-polymerizing process of my invention is extremely well suited to combination with a reforming unit of this character, it will be understood by those skilled in the art that my process may be employed in conjunction with other types of oil-cracking operations, for example those operated for the purpose of obtaining gasoline and gases from relatively heavy oils such as gas oil, reduced crude andthe like. Referring now specifically to the drawing, an oil to be cracked, such for example as a naphtha of relatively low anti-knock value and, it may be, a naphtha having a slightly, higher end boilingpoint than that oi' the desired final motor-fuel` product, or a relatively heavy oil, such as gas oil,

-is introduced by means of a pump I and a line 2 wherein is located a heat-exchange coil 3 into a heating coil 4 located within a suitable heating furnace 5. As the oil passes through the -coil 4, it is subjected to a cracking temperature of, for example, from 850 to l050 F. and preferably in the instance illustrated to a temperature of vabout 975 F., under a pressure preferably in excess of 100 pounds persquare inch. for example about 800 pounds per square inch or higher, for a sufficient period of time to insure the desired degree of cracking of the oil. Where naphtha o1' low anti-knock value is used as charging stock, cracking is effected merely to such extent as to effect a material increase in the anti-knock values, without materially changing the boiling kpoint range, but on account of the rather refractory nature of naphtha, fairly high cracking temperatures are necessary and the production of a `considerable amount of gas is practically inevitable'.

The heated products from the pipe coil 4 then pass through a transfer line 6 wherein is located a.' pressure-reducing valve 1 into an evaporator 8 maintained at a lower pressure than that obtaining in the coil 4. By way of example, in the present instance, in which a pressure of 800 pounds per souare inch is maintained in the coil 4, the evaporator 8 may be maintained at a pressure of 300 pounds per square inch or higher.

The evaporator 8 may be provided. as illustrated, with suitable baiiies 9 and with cooling means such as a line I0 wherein is located a. pump II forvintroducing a suitable hydrocarbon oil. As the products from the transfer line 8 enter the evaporator 8, volatile portions `thereof are liberated, and residual portions are withdrawn from the bottom of the evaporator 8 i through a valved line I3. Where desired, residual oil or tar Withdrawn through the line I3 may be ashed at a lower pressure in a suitable tar flasher (not shown) and distillate thus produced may be returned to the cracking system as, for example, by way of the line I0.

Vapors pass from the evaporator 9 to a fractionating column I5, the'interior of which is provided with suitable plates or trays IG and wherein may be located the heat-exchange coil 3. Passing upward through the fractionating column I5, the vapors are subjected to partial condensation and fractionation for the purpose of condensing andl removing constituents heavier than the desired final gasoline product. A portion of the condensate thus obtained is removed from the i trap-out tray I4 through a line I8, wherein may be located a pump I9, and delivered through a branch line 20 having a valvel 2I to the transfer line 6 where it is employed for the purpose of quenching the hot products from the coil 4 to a temperature below an active cracking temperature, for example from about 750 to 850 F'. Condensate withdrawn through the line I8 inexcess of that required for quenching the products from thecoil 4 is delivered through a-line 22 having a valve 23 to the line 2 as recycle stock .4 for the coil 4.

The fractionated overhead vapors from the fractionating column I pass through a vapor line 25 to a condenser 26 operated approximately at atmospheric temperature or at any rate employing as a cooling medium water at atmospheric temperature or a little below, and the partially condensed products then pass through a line 21 to a gas separator 28 preferably.main tained under a pressure slightly below that obtaining in the fractionating column I5, for example about 290 pounds per square inch.

In the separator 28, gasoline condensate separates from uncondensed gases. If the pressure in the separator is high enough, the separated gases may consist substantially entirely of hydrogen and methane; at lower pressures, higherboiling constituents may separate in gaseous form. 'I'he condensate passes through a line 29 wherein may be located a' pump 38 to a gasoline stabilizer or rectifying column 35 provided with suitable plates or fractionating trays 36, a cooling coil 31 and a heating coil 38. The stabilizer 35 is operated for tbe purpose of removing constituents from the condensate which are too light to be included in the final gasoline product, and is preferably held under a superatmospheric pressure at least not materially below that obtaining in the separator 28, for example about 280 pounds per square inch or higher. Stabilized gasoline is withdrawn from the bottom of the stabilizer 35 through a valved line 39, while overhead vapors pass through a vapor line to a condenser 4I and thence through a line 42 into an accution before being subjected to conversion. If,`

however, the gases rem'oved from the separator 28 contain substantial amounts of constituents such as propane, propylene, butane and butylene, they maybe fractionated separately to recover these constituents for conversion or they .may be delivered to the accumulator` 43 and mixed with overhead or refiux from the stabilizer prior to fractionation, or they may be delivered by means of a valved line 45a to the stabilizer 35.

In the latter instance, gases are withdrawn from the accumulator 43 through aline 60 and compressed by means of a pump or compressor 6i to a relatively high pressure of for example from 300 to 500 pounds per square inch. The heat of compression may be removed by means of a cooler 62 located in the line 60. The compressed gas then passes through the line to a gas stabilizer, fractionator or rectifier 63. Liquid from the accumulator 43 is delivered to a lower point in the gas stabilizer 63 through a i line 4 wherein is located a pump 85, by means of which such condensate is also placed under a pressure of vfrom 300 to 500 pounds per square inch, or whatever pressure is maintained in the stabilizer 63. A cooler 66 may be provided in the line 60 if so desired.

The gas stabilizer 63 is internally provided with suitable plates or trays 10 and with a heating coil 1| located in the lower portion thereof. Bottoms from the tower 63, comprising principally liquefied butane, as well as heavier hydrocarbons, such as pentane, if present, are Withdrawn therefrom through a, line 12 wherein is located a pump 13, and aiter being passed through a cooler 14 are returned to the upper portion of the tower 03 as a reiiuxing and absorbing medium. `The cooler 14 is preferably operated in such manner as to eiiect cooling of the constituents thus returned to a temperature not above atmospheric and preferably lower, for example, from 0 C. or even lower to 10 C. Fixed gaseous constituents, comprising principally hydrogen and methane, are withdrawn from .the top of the gas stabilizer 63 through a valved line 15. The operation of the stabilizer 63 is so conducted that gases thus withdrawn comprise substantially all vof the hydrogen and methane but are substantiallyfree from higher constituents,` and at any rate preferably do not contain more than 10% of the convertible unsaturated constituents.

LWhere desired, .the gases removed at 15 may be scrubbed with a suitable solvent such as gas oil to recove'i` butane and the like therefrom, the

latter being recovered from the enriched solvent and returned'to the gas fractionator.

By means of a Weir 16 located`at an intermediate portion of the gas-stabilizer 63, reflux is withdrawn as a side stream through a line 11 and passes to a stripper '|8having plates or trays 18 and heating means such asthe coil 80 located therein, and wherein any hydrogen, methane and excess ethane Acontained in the side stream thus lwithdrawn is driven off and returned lto the gas-stabilizer 83 through a line 8|. The stripped compressed liquid, consisting principally or entirely of propane, propylene. butane and butyl'ene, but sometimes containing some ethane and ethylene as well as pentane and heavier hydrocarbons.- then passes through a line 82 to a Y ltank 88. l

`While I have illustrated and described a preferred type of gas-fractionating system, it will be understood that 4my invention in its broader aspects is not limited to the use ofthe particular'type illustrated,.as the fractionation of the gases prior to conversion thereof may be accomplished in other suitable manners, if desired. The type of operation illustrated is, however, well adapted for use in the processof my invention.

Before subjecting the hydrocarbons collected in the tank 83 to polymerization, it may prove highly desirable to remove hydrogen sulphide therefrom, for the reason that if hydrogen sulphide is permitted to pass in any considerable amount with the hydrocarbons through the polymerizing zone it will tend to be chemically combined with the hydrocarbons resulting from the polymerization treatment, and would result in a flnal gasoline product difficult to treat for removal of sulphur impurities.- In the instance disclosed in Fig. 1, I have illustrated, by Way of example, means for removing hydrogen sulphide comprising an absorber wherein the gases are subjected to contact with a suitable chemical Jadsorbent having the property of chemically'l combining with and removing hydrogen sulphide from the hydrocarbons.

v Hydrocarbons collecting in the tank 83 may pass by way of a line 84, wherein may be located a pump 85 and valves 88 and 81 to a scrub- 'ber |04. f

As the hydrocarbons pass vupward through the scrubber. |04 they are subjected to countercurrent contact with a flow of a suitable hydrogensulphide absorbent, such for example as an aqueous solution of sodium hydroxide, sodium carbonate, or any othersuitable agent, introduced into the upper portion of the scrubber |04 through a line |05 wherein may be located a pump |06. The scrubber |04 may be provided, as shown, with a plurality of baiiles |06 or other suitable gas-and-liquid-contact devices for-.promoting efiicient contact between the hydrocarbons and the liquid washing medium; Spent washing medium is removed from the bottom of the scrubber |04 through a valved line |01, while the hydrocarbons thus freed wholly or to the desired extent from hydrogen sulphide pass through l a line ||0 to a pump I for compression.

By regulating-the pressure onjthe hydrocarbons undergoing treatment, as for example by means of the valve '81 and the compressor 85,

cible therewith and may readily be separated therefrom. Instead .of employing a-solution of caustic soda, I may employ various solutions, .preferably also of an alkalinev character such Yfor example as a solution of sodium carbonatephenolate, or thioarsenate. The latter solutions have the advantage over caustic soda `solutions in ythat they may readily be regenerated and reing hydrocarbons on the other hand is effected in the separator 28, and the gases separated at this point can therefore be removed from the system, or where the gases separated in the separator 28' are removed from the system at that point for any reason, regardless of their nature, and the material supplied to the accumulator 43 is sufliciently free from hydrogen and methane (by reason of prior fractionation or separation), then the' fractionator 53 may be omitted and the material from the accumulator 43 may be delivered directly through a line 90 having a valve 9| and the line 84 or the line ||2 `to the absorber |04 or the compressor respectively, as desired. A compressori 92: may be located in the line 90, for use where necessary or desirable.

The hydrocarbons passing through the line I are compressed by means of the pump to a pressure of from 500 to 3000 pounds per square inch and preferably from about 800 to 1000 pounds per square inch, and then pass by way of a line |20 to a heat exchanger |2|, and thence by way of a line |22 to a heating coil |23 1ocated within a suitable furnace |24. Here the compressed gases are heated to a temperature at which active polymerization takes place. While I prefer to employ temperatures of from 1000 to 1100 F., somewhat higher or lower tempera- .-tures may be employed if desired. However, temperatures lower than '750 F. and higher than 1250 F. are ordinarily not desirable or advantageous. The hot products then pass through a line |25 to the heat-exchanger or soaker |2| where they are soaked for a suiiicient period of time, for example 90 seconds (total time of contact in heating coil and soaker) to effect the desired degree of conversion'.

In general, higher pressures and high olefincontent favor lower temperatures and vice versa. If catalysts are employed, considerably lower temperatures maybe used, depending upon the particular catalyst employed as well as the other factors of operation. l

Ordinarily, I have found that, in operating in the manner set forth herein, the reactions taking place in the soaking coil |2I are not highly exothermic in character, but may be slightly so,

-and the heat exchanger or soaker |2| is ordif nariLv so operated as to effect, at least in the first stages thereof, merely a balancing of such exothermic reactions as may occur, and to maintain the gases at the desired active polymerizing` temperature for a sufcient soaking period. In the latter stages of the soaker |2 I, however, considerable cooling may be effected even to a point materially below an active polymerizing temx The latter pass-from the soaker |2| through a line |28, wherein may be located a cooler or condenser |2'|, preferably operated at atmospheric temperature or thereabout, into av high-pressure separator |28, which is preferably operated at a pressure not materially lower than that obtaining in the coil |23. Here a separation of liquid products of polymerization from unpolymerized gases occurs, the liquid polymers comprising principally liquid boiling within the general boilingpoint range of gasoline or motor fuel being withdrawn through a line |29 wherein is located a valve |30, while the uncondensed gases are withdrawn through a line |3| wherein is located a valve |32. withdrawn through the line |29 are returned to the oil-cracking unit for recovery. Thus, as illustrated in the drawing, these products may be introduced into the line 8 ahead of the pressurereducing valve 1, to pass with the products from the coil 4 into the evaporator 8. Operating in this manner, the liquid thus introduced into the line 6 serves as a quenching medium Vfor the products passing therethrough, and the gasolinelike constituents recovered from the polymerizing operation are condensed at 28 and stabilized in the stabilizer 35. It will be obvious, however, that a separate fractionating and condensing system, and if necessary a separate stabilizing system, may be employed if desired.

In any event, the fixed gases produced in` the gas-polymerization operation are fractionated to remove hydrogen and methane and recycled to the gas-polymerizing operation. As shown in the drawing, this may be accomplished in one of several manners; the gases may be delivered through a branch line |40 having a valve |4f to the line 21 and thence into the separator 28, or, where the products withdrawn from the accumulator 43 are fractionated, as at 63, prior to conversion, they may be delivered to the accumulator 43 through a line |42 having a valve |43 and communicatingwith the line 42 which leads to the accumulator 43. In this instance, these gases traverse the gas-fractionating tower 63 together with gases produced in the oil-cracking unit and are fractionated before being returned to the coil |23.

4As a further alternative, where hydrocarbons from the accumulator 43 are to be passed directly to the conversion system through the line. 80, the overhead products from the separator |28 may be passed through a branch line |50 having a valve to a suitable fractionating device indicated diagrammatically at |52, for removal of hydrogen and methane. as well as ethane to the desire?, extent. The thus separated nxed gases ar fre- 4moved at |53 while the fractionated recycle stock then passes to the accumulator 43 through a line |54 having a' valve |55 an`d communicating with the line |42. In this instance, the valve |32 'is closed'. Obviously, various types of gas-frac- In this instance, the liquid products tionating means may be employed for this purpose.y Alternatively, the liquid products from the conversion .operation may be condensed under pressure, separated from fixed gases, and stabilized, the overhead from the stabilizer then passing tothe accumulator 43.

While I have illustrated in the drawing a soaking coil |2| it will be understood that enlarged soaking chambers may be employed, if desired. However, I have found that the best results are obtained when both the heating coils and the soaking coils are constructed of relatively small diameter tubing.

'I'he polymerized gasoline produced in accord- 'ance with the process of our invention represents a very advantageous and valuable product. The anti-knock value of this gasoline is exceptionally high, for example, above 80 in octane rating, but l it is predominantly non-aromatic. It will be understood by those skilled in the art that the gasoline recovered 'from the stabilizer 3l of Fig. 1 will, of course, contain a considerable proportion of cracked or reformed gasoline, and consequently may not be expected to have as high an antiknock value as that of the polymerized gasolinelike product alone. In fact, the gasoline recovered from the stabilizer of Fig. 1 represents a blended product,l containing both cracked and polymerized gasoline, and consequently partakes of the characteristics of each.

While I 'have described my invention hereinabovewith respect to various specificy operating examples and details, it will readily be understood by those' skilled in theart that my invention is not limited to such illustrative details or examples but may variously be practiced and embodied within the scope of the claims hereinafter made.

. I claim:

1. The V`process of obtaining normally liquid low boiling hydrocarbons suitable for use as motor fuel from hydrocarbon oil which comprises subjecting said hydrocarbon oil to pyrolytic conver- Vsion treatment to form hydrocarbons suitable as gasoline constituents, separating from the products of said conversion treatment a gaseous fraction containing hydrogen and methane and satu- `rated and unsaturated hydrocarbons having two to four carbon atoms per molecule, introducing said gaseous fraction into a fractionating zone at a point intermediate the upper and lower portions thereof, fractionating said gases in said zone into a xed gas fraction predominating in hydrogen and methane and a liquefied gas fraction predominatlng in hydrocarbons having two to four carbon atoms per molecule, withdrawing a liqueiied side stream from said fractionating zone at a point intermediate the upper and lower portions thereof, heating the lower portion of the fractionating zone to strip light constituents from the liquefied gases contained therein, withdrawi ing said liquefied gases stripped of light constituents from said lower portion of said fraction- -ating zone, cooling said withdrawn liqueed gases, introducing said cooled liquefied gases into the upper portion of said fractionating zone whereby said cooled liquefied gases pass downwardly through said fractionating zone in intimate contact with the gases ascending said fractionating zone to effect condensation and absorption of hydrocarbons having two to four carbon atoms per molecule, separately subjecting said side stream to elevated temperature and superatmospheric pressure to effect conversion thereof to normally liquid products including gasolinelikeL material, separating the products of said last- -mentioned conversion operation into a normally liquid fraction and a normally gaseous fraction, admixing said last-mentioned normally liquid fraction with the products of pyrolytic conversion of said hydrocarbon oil whereby cooling of said products is effected and, said normally liquid fraction 'is fractionated with said products oi' pyroytic conversion, and returning said normallygaseous fraction from said gas conversion operation tojsaid fractionating zone for separation'V intoa fixed gas fraction and a liquefied gas fraction as described. y

2. The methodY in accordance with claim 1 wherein said first-mentioned gaseous fraction is rst separated into a liquefied fraction and a gaseous fraction, said liquefied ,fraction is introduced into said fractionating zone at an intermediate point adjacent the lower portion thereof I and said gaseous fraction is introduced into said fractionating zone at an intermediate point adjacent the upper portion thereof.

3. The method in accordance with claim 14 wherein said liqueed side stream is heated externally of said fractionating zone to strip light constituents therefrom, said light constituents are returned to said fractionating zone at apoint intermediate the upper and lower portions thereof, and the remaining liquefied portion stripped fraction into a fractionating zone at a point intermediate the upper and lower portions thereof,

fractionating said gaseous fraction in said zone into alight gas fraction and a liquefied gas fraction predominating in hydrocarbons having two to four carbon atoms per molecule, withdrawing a liquened side stream from said fractionating zone at a point intermediate the upper and lower portions thereof, heating the liquefied gases collected in the lower portion of the fractionating zone to strip therefrom light constituents, with- @drawing said liquefied gases stripped of' light constituents from said fractionating zone, cooling said withdrawn liquefied gases, introducing said cooled'liqueed gases into the upper portion of said fractionating zone whereby said cooled liquefied gases passdownwardly through said fractionating zone in intimate contact with the` gases ascending said fractionating zone to effect condensation and absorption of hydrocarbons having two to four carbon atoms per molecule, sepav rately subjecting said withdrawn .side stream to polymerizing conditions of temperature and' pressure to effect conversion thereof to normally liquid products including gasolinelike material, and admixing the normally liquid product of said polymerization treatment and normally s eous products of said polymerization treatment including hydrocarbons having two to four carbon atoms per molecule with the products of said hydrocarbon oil conversion treatment-during the fractionation thereof whereby the said gasolinelike constituents of the polymerization products of, and the remaining liquefied portion strippedv of light constituents is passed to said polymerization treatment.

7. A process of producing normally liquid gasolinelike hydrocarbons fromnormally gaseous hydrocarbons which comprises passing normally gaseous hydrocarbons comprising saturated and unsaturated constituents of from two to four carbon atoms per molecule through a heating zone and subjecting said hydrocarbons to elevated temperatures and pressures to effect polymerization thereof into gasolinelike constituents, cooling said products of polymerization, separating the products of said polymerization into ay gaseous fraction and a liquid fraction, passing said gaseous fraction directly into an enlarged zone having upper and lower sections, subjecting said gaseous fraction in the upper section of the enlarged zone to rectiilcation and scrubbing, flowing liqueed constituents of said gaseous fraction into the lower section of said enlargedzone, heating the said liqueiied constituents in the lower* section of said enlarged zone to strip therefrom lowboiling hydrocarbons and to leave a residue consisting primarily of relatively high-boiling normally gaseous hydrocarbons, passing liquid constituents thus lstripped of low-boiling materials to the upper section of said enlarged zone in liquid condition as scrubbing medium, removing hydrogen and methane from the upper section of said enlarged zone, withdrawing a liquefied fraction consisting primarily of hydrocarbons having from two to four carbon atoms per molecule from a point intermediate the upper and lower sections of said enlarged zone, and passing hydrocarbons thus withdrawn to said heating zone.

8. 'I'he method in accordance with claim 7 wherein the liquid fraction separated from the 55 vhydrocarbons which comprises passing normally gaseous hydrocarbons comprising saturated and unsaturated constituents of from two to. four carbon atoms per molecule to a heating zone and subjecting said hydrocarbons to elevated temperature to effect polymerization thereof into gasolinelike constituents, fractionating'the products of polymerization to separate therefrom a normally liquid fraction including gasolinelike constituents and a normally gaseous fraction containing saturated and unsaturated hydrocar,

gas fraction and a liquefied gas fraction pre- Y dominating in hydrocarbons having from two to four carbon atoms per molecule, withdrawing a liqueed side stream from said fractionating zone at a point intermediate the upper and lower portions thereof, passing the side stream thus withdrawn to said heating zone, heating the liqueed hydrocarbons collected in the lower portion of said fractionating zone to strip light constituents from the liquefied gases, withdrawing said liqueed gases stripped of light constituents from the said fractionating zone, cooling said withdrawn liquefied gases, and introducing said cooled liqueed gases into the upper portion of said frac- 'tionating zone whereby said cooled liquefied gases pass downwardly through said fractionating zone in intimate contact with the gases ascending said fractionating zone to effect condensation and absorption of hydrocarbons having two to four carbon atoms per molecule.

10. The method in accordance with claim 9 wherein said mst-mentioned gaseous fraction is rst separated into a liquefied fraction and a gaseous fraction, said liquefied fraction is introduced into said fractionating zone at an intermediate point adjacent the lower portion there-A of and said gaseous fraction is introduced into said fractionating zone at an intermediate point adjacent the upper portion thereof.

11. The method in accordance with claim 9 wherein said liquefled side .stream is heated externally of said fractionating zone to strip light constituents therefrom, said light constituents are returned to said fractionating zone at a point intermediate the upper and lower portions thereof, and the remaining liquefied portion stripped of light constituents is passed to said polymerizing treatment.

PERCIVAL C. KEITH, Jn. 

